Monoazo dyestuffs



United States Patent 3,392,164

Patented July 9, 1968 1 ably carried out in the presence of dispersing compounds. 3,392,164 In order to accelerate the dyeing, swelling agents may be MONOAZO DYESTUFFS add-ed to the dyeing bath; dyeing can also be carried out at Hermann Wunderlich, Cologne-Mulheim, Germany, as-

signor to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany higher temperatures and in closed vessels, if desired.

The new dyestuffs are likewise useful for the dyeing of No Drawing. Ffled June 16 1964, Ser. 375,662 other hydrophobic textile mater als, such as textiles made I Claims priority, application Germany Oct 4 1963, from aromatic polyesters, particularly polyethylene ter- 91 ephthalates and polyesters from terephthalic acid and 1,4-

Claim (Cl, 260-453) bis-hydroxymethyl cyclohexane, cellulose triacetate and 1 superpolyamides. Dyeings with very good to excellent r V fastness properties are obtainable on those materials. ABSTRACT OF DISCLOSURE {The following examples are given for the purpose of Monoazo dyestuffs of the formula illustrating the inventiomParts given are parts by weight.

RC-----N Example .1

- H P; 2.7 parts of 5-amino-3-phenyl-thiadiazole-1,2,4 are dissolved in 35 parts of 90% phosphoric acid and treated s with 4.6 parts of nitrosyl sulphuric acid at 0-5 C. After wh in R is lower y p ny r n p y A is a stirring the mixture for a further 4 hours at this tempera- 1-aryl-3-alkyl-pyrazolone-5 joined to the azo group in the tune, a small amount of excess nitrite is removed with 4-P05iti0n Of a Y Y y amine joined to the 320 amiido-sulphonic acid and a solution of 2.53 parts of group in the 4-position; the dyestuif being free of sul- 1-';'1 1-3. h 1 l -5 i .2() art f dil t hy Phonic acid and carboxylic acid groups. The dyestuffs of dr ochloric acid is added dropwise at O5 C. Within 10 this invention are suitable for dyeing and printing synminutes. Stirring is continued for a half hour and the th i fi s, p i y n zin pp and reaction mixture is then poured on 300 parts of ice. It is nesium-modified polypropylene fibers. then buffered with a dilute sodium hydroxide solution to a pH value of 5. The precipitated dyestuff has the constitution.

The present invention concerns water-insoluble, metalfree azo dyestuffs of the general formula N z 7 l1 (Likes \S N N H cm Herein A means the radical of a 1-aryl-3-alkyl-pyrazof loneS linked in the 4-position, or the radical of a 3-hydroxydiaryl amine linked in the 4-position; R stands for an aromatic or aliphatic radical. The radicals A and R do not contain any sulphonic acid or carboxylic acid groups, but may otherwise contain any non-ionic substituents, such as 40 hydroxyl, alkoxy, halogen, cyano, acylamino, al-kyh nitro, P Z B i f of fihi il g. formulgare 4 trlilfiuoroaltyl,1 SgllPhOfllOlldE, carboxylic acid ester, sul- 53:; on; partpzgf sg'gqbwzceiizvagd geld 0H;Spa;r?oSapi :;;1a p onic an su p onami e groups.

The new azo dyestuffs are produced by coupling a thalene sulphonic acid/ formaldehyde condensation proddiazotized 5-amino-3-aryl or -alkyl-1,2,4-thiadiazole with j 10 Parts of polyprPPylene fibre Yam are dyed here a 1 ary1 3 a1ky1 pyrazoloned or a 3 hydroxy diaryl amine with for one hour at 'blll'lng temperature. After a weakly each time in the 4 position, choosing the initial compo alkaline aftertreatment at 4050 C. with 0.5 parts/litre nents in such a manner that the final dyestuif contains no of commerclzfl detergent followed by i an Orange sulphonie acid or earboxyhe acid groups dyeing is obtained with very good fastness to solvents, The Starting components are coupled in an acid neutral 5 rubbing, sublimation,.. wet processing, waste gas and light.

to weakly alkaline aqueous,anorganic or organic-aqueous Polypropylene fibres used tl'le exallll31e medium, and the dystufis obtained which are hardly sohb: tamed, apart from other usual additives, nickel phenolate ble or insoluble in water are separated by usual methods. of b1s(a1kY1Ph n01)-IT10I1SI11Ph1de$ 1n coflcentratlons 0f Suitable diazo components are, for example 5-amino-3- Spun, Into themmethylthiadiazole-1,2,4; 5-amino-3 phenyl thiadiazole 55 If, instead of the am P P 1, t am 1,2,4? and 5 amino 3 (ymhwphenyl) thiadiazo1e 1,2,4 components of the following table are used, dyeings on and the 5 amino 3 methyl thiadiazol ly2j4 7 these nickel-modified polypropylene fibres are obtained As azo components from the pyrazelone Series which likewise have very good general fastness properties. may be mentioned: 1 phenyl-3 methylpyrazolone 5, Shade on modified l-(2',5-dichlorophenyl)-3-methylpyrazolone-5, 1-(4'-ni- A20 component; trophenyl)-3-methylpyrazolone-5 and from the 3-hydroxydiarylamine series: 3-hydroxydiphenylamine, 3-hydroxy-Z-methyldiphenylamine, 3-hydroxy 4 ethoxydi phenylamine and the like.

polypropylene fibre 1-(3'-chlorophenyl)-3-methylpyrazolone-5 Orange l-(2',5'-dichlorophenyl)-3-methylpyrazolone- 5 Orange' 1-(4'-nitrophenyl)-3-methylpyrazolone-5 Oran e The new d estuffs are excellentl suitable for the d eing and prinzing of synthetic fibr es, especially nickel, 'Sulphonamldophenyl)'3'methylpyrazo' i e, copperand magnesium-modified polypropylene, lone's Orange fibres. These polypropylene fibres contain the aforesaid Example 2 metals spun into them in form of phenolates, fatty acid salts, heterocyclic complexes, dialkyl-dithio-carbamates or A 11310 501mm Prepared accoffillng to p 1 from inorganic salts or complex compounds. Since the dyestuffs Parts of -P y 1S C01 are hardly soluble or insoluble in water dyeing is preferbined with a solution of 2.7 parts of 3-hydroxy diphenyl 3 A amine in 30 parts of 60% sulphuric acid at C. The reaction mixture is stirred for 30 minutes at 5 C. and is then poured on 300 g. of ice. It is then buffered with a dilute sodium hydroxide solution and ice to a pH of 5. The precipitated dyestuif has the following constitution.

100 parts of polypropylene fibre material in the form of a combed material are dyed in 2000 parts of water which has been adjusted with dilute sulphuric acid to a pH of about 4-5 and, apart from-4 parts salicylic acid methyl ester,-also contains 4 parts of a weakly anion-active alkylphenyl polyglycol ether sulphate, with one part of the finely dispersed dyestuif of the above constitution for one hour at'100 C.

The resulting violet dyeing is distinguished by very good fastness to wet processing, sublimation, solvents, waste gas and light.

Equally valuable violet dyeings on polypropylene fibres modified with nickel phenolates or zinc dithiocarbamates are obtained if the azo component of this example is replaced by 3-hydroxy-2-methyldiphenyl amine, S-hydroxy- 4'-methyldiphenyl amine and by 3 -hydroxy-4'-ethoxydiphenyl amine.

Example 3 1.8 parts of 5-amino-3-methyl-thiadiazole-1,2,4 are dissolved in 30 parts of 90% phosphoric acid and diazotized within 4 hours with 4.6 parts of nitrosyl sulphuric acid at 05 C. After a small amount of excess nitrite has been destroyed a solution of 3.5 parts of 1-(2',5'-dichlorophenyl)-3-methylpyrazolone-5 in 30 parts of dilute hydrochloric acid is added dropwise at 0 C. The reaction mixture is stirred for 30 minutes, then poured onto 300 parts of ice and buttered with dilute soda lye to a pH value of 5.

The precipitated dyestulf has the formula 0.2 parts of this dyestutf are used according to the instructions of Example 1 for the dyeing of nickel-containing polypropylene fibres. A yellowish orange dyeing is obtained which exhibits very good fastness to solvents, rubbing, sublimation, wet processing and light.

If instead of the azo component of this example the azo components listed in the following table are used dyeings on nickel-modified polypropylene fibres are obtained which likewise possess very good general fastness properties.

If S-amino-3-(3'-nitrophenyl)-thiadiazole-1,2,4 is used as diazo component the dyestufi of the formula is obtained. It dyes polypropylene fibres which contain metal compounds, e.g; nickel phenolatesg'zinc or nickeldithiocarbamates, in combination with stabilizers spun into the fibres orange shades with excellent general fastness properties. The dyeing conditions correspond to those of Example 2.

I claim:

1. -A monoazo dyestuif of the formula wherein R represents a member selected from the class consisting of lower alkyl, phenyl, and nitro phenyl, A stands for a member selected vfrom the class consisting of wherein X is phenyl or phenyl substituted with one or two substituents from the group consisting of chlorine, nitro, and sulfonamide; and Y is phenyl or phenyl substituted with methyl or ethoxy; the dyestuff being free of sulphonic acid and carboxylic acid groups.

2. The dystuif of the formula 8,392,164 6 4. The dyestufr' of the formula 8. The dyestuff of the formula 9. The dyestufi of the formula I CH3 10 N S -NNl CH3 -NO2 N 5. The dyestuff of the formula I N 10. The dyestufi of the formula I -N 01 II 11102 JN=N Fc H3 Cl 5 Q] N 6. The dyestufii of the formula 7. The dyestufi of the formula UNITED STATES PATENTS 2,791,579 5/1957 Taube 260-158 HO 2,871,231 1/1959 Straley et a1 260-158 X l CHARLES B. PARKER, Primary Examiner.

s D. M. PAPUGA, Assistant Examiner.

Patent No. 3,392 ,164

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION July 9, 1968 Hermann Wunderlich It is certified that error appears in the above identified patent and that said. Letters Patent are hereby corrected as shown below: Column 2, line 18, "0-5 C." should read 0-5 C. line 46, "billing" should read boiling Column 4, lines 65 to 70, the portion of the formula reading I N I should read N J N J- Signed and sealed this 13th day of January 1970.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Edward M. Fletcher, J r.

Commissioner of Patents Attesting Officer 

